EP2546295A1 - Masses de formage thermoplastiques dotées d'une stabilité améliorée contre le vieillissement thermique - Google Patents

Masses de formage thermoplastiques dotées d'une stabilité améliorée contre le vieillissement thermique Download PDF

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Publication number
EP2546295A1
EP2546295A1 EP11174032A EP11174032A EP2546295A1 EP 2546295 A1 EP2546295 A1 EP 2546295A1 EP 11174032 A EP11174032 A EP 11174032A EP 11174032 A EP11174032 A EP 11174032A EP 2546295 A1 EP2546295 A1 EP 2546295A1
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Prior art keywords
metal
thermoplastic
molding compositions
compound
thermoplastic molding
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EP11174032A
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German (de)
English (en)
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EP2546295B1 (fr
Inventor
Tobias Benighaus
Detlev Joachimi
Günter Margraf
Christian Ruthard
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • the present invention relates to thermoplastic molding compositions containing as a stabilizer system against heat aging finely divided particles containing a metal 1 and a compound of a metal 2 with at least one further element where a) metal 1 is less noble than metal 2 and b) the particles are constructed so that metal 1 and the compound of the metal 2 with at least one other element in contact with each other and the use of the described stabilizer system for improving the heat aging behavior of thermoplastic molding compositions and articles which are produced from these molding compositions.
  • Thermoplastic molding compounds generally show a deterioration in their mechanical properties when exposed to elevated temperatures over an extended period of time. This effect is based primarily on the oxidative damage of the polymer.
  • a longer period in the sense of the present invention means longer than 100 hours, elevated temperatures in the sense of the present invention means higher than 80 ° C.
  • thermoplastic molding compounds against heat aging is therefore usually assessed by comparing mechanical properties, in particular the impact strength or the tensile strength before and after heat aging at a defined temperature over a defined period of time. Since the oxidative damage of the polymer is often associated with a loss of mass, in the cases in question, this value can also be used to assess the stability against heat aging.
  • DE-4305166 A1 describes an improvement in the copper-based thermal stabilization by adding strong reducing agents, which leads to in situ formation of finely divided elemental copper. It is also shown in this application that colloidal elemental copper that is not generated in situ has significantly lower activity.
  • WO2005 / 007727 A1 describes the use of finely divided elemental iron as a thermal stabilizer. This is superior to the hitherto conventional copper-based thermal stabilizers. An in situ reduction of iron is said to be through the process that takes place in WO2005 / 007727 A1 can be avoided by adding the elemental iron in the form of a fine powder having a mean weight-average size of at most 450 microns.
  • base metals such as iron are oxidized superficially quickly by atmospheric oxygen even at normal ambient temperature. As a result, the surface of the individual metal particles is coated by an oxide layer, which reduces the activity of the metal particles as oxygen scavengers and therefore limits their use as thermal stabilizers.
  • base metals are metals which react with the oxygen from the air under normal conditions, oxidize them. This applies to iron, zinc or aluminum.
  • base metals are therefore metals whose redox couples have more negative standard potentials than the normal hydrogen electrode.
  • fine metal powder is also problematic from a safety point of view. Even base metals react under normal conditions only slowly with atmospheric oxygen. For the function as oxygen scavenger a high surface-to-weight ratio is advantageous. However, under these conditions, many metals, including iron, become pyrophoric. Therefore, with the use of fine metal powders, the risk of metal fires and dust explosions is high. This phenomenon is described in the literature for iron, for example in the textbook of inorganic chemistry, 101st edition, Hollemann, Wiberg, deGruyter, 1995, 1511-1514.
  • metal salts or other suitable metal compounds in the polymer melt with reducing agents, for example hypophosphite salts or salts of dithionic acid.
  • metal salt and reducing agent must be reacted in the polymer melt. Due to possible side reactions with the thermoplastic and / or the formation of gaseous components, the Reducing agents are introduced into the melt only in small concentrations. Therefore, it is difficult to ensure the generation of a sufficient amount of metal for thermostabilization of the thermoplastic by reduction.
  • the present invention therefore an object of the invention to provide a stabilizer for thermoplastic molding compositions, which improves the stability against heat aging over the known extent and avoids the disadvantages mentioned above.
  • thermoplastic molding compositions containing as a stabilizer system, especially against thermo-oxidative degradation, finely divided particles containing an elemental metal 1 and a compound of a metal 2 with at least one further element, characterized in that metal 1 is less noble than metal 2, and the particles are constructed so that metal 1 and the compound of metal 2 are in contact with at least one other element.
  • the invention also provides a process for producing thermoplastic molding compositions comprising the stabilizer to be used according to the invention and components to be produced therefrom, preferably components for motor vehicles, particularly preferably components for the engine compartment of motor vehicles.
  • Particles are then finely distributed in the sense of the invention, if they have a mean particle size d 50 of at most 500 microns in the matrix, with each particle agglomeration without matrix between the interfaces of the individual particles is considered as a total particle for the calculation of the d 50 value.
  • such elements are used as the metal 1, which are capable of chemically reducing the compound of metal 2 with at least one further element.
  • metals 1 which are less noble than metal 2.
  • Metals 1 to be used are therefore those whose normal potential is lower in elemental form at 25 ° C. relative to the standard hydrogen electrode.
  • metal 1 is the metals of groups 1, 2, 3, 4, 12 and 13 of the Periodic Table
  • metals of the series Li, Be, Na, Mg, K, Ca, Sc, Ti, Sr, Zr , Zn, Cd, Hg, B or Al used as metal 1.
  • metal 1 metals of groups 12 and 13 of the periodic table In particular, most preferably aluminum is used as the metal 1.
  • Metals of the series Cr, Mn, Fe, Co, Ni or Zn particularly preferably metals of the series Fe, Co, Ni or, Zn and very particularly preferably iron, are preferably used as metal 2.
  • metal 2 is only reduced in-situ to the elemental metal 2 in the thermoplastic melt and is previously present as a compound with at least one further element which is in contact with metal 1.
  • metal 2 is in combination with a halogen and / or oxygen.
  • the compound of metal 2 with at least one further element is particularly preferably iron (III) oxide.
  • a thermoplastic melt is present in the processing operation of the thermoplastic molding compositions according to the invention, if they are processed by extrusion, blow molding or injection molding.
  • the particles of the stabilizer according to the invention may have different shapes, which have a contact between metal 1 and the compound of metal 2 with at least one further element.
  • the contact between the two components can be direct, with both components having at least one common interface, or indirectly, when the two components are connected by electrically conductive material.
  • Preferred forms according to the invention with a direct contact between the two components of the stabilizer according to the invention are either particles which consist of a core of metal 1, which at least partially with the compound of metal 2 with at least one other Element is coated or platelets, which consist of two layers, wherein one layer of metal 1 and the other layer consists of the compound of metal 2 with at least one further element.
  • particles which consist of a core of electrically conductive material which is at least partially coated with metal 1 and the compound of metal 2 with at least one further element.
  • the stabilizer system to be used according to the invention is preferably used as powder, paste or compactate.
  • Preferred powders of the stabilizer system to be used according to the invention have an average particle size d 50 of at most 500 ⁇ m, preferably 1 to 250 ⁇ m, particularly preferably 5 to 150 ⁇ m (according to ASTM D 1921-89, method A), whereby the fine distribution in the thermoplastic is ensured .
  • the binders customarily used for the production of pastes or compactates preferably waxes, oils, polyglycols or similar compounds, can be used in suitable proportions.
  • a particularly preferred according to the invention to be assigned stabilizer system is aluminum powder of Fe 2 O 3 coating, the BASF SE is available as a paste in gasoline as Pallocrom ® Gold L 2020 or Pallocrom ® Orange L 2800th
  • a batch of stabilizer system can be used with a polymer.
  • a continuous phase is referred to as a spatially connected region with the same or not abruptly changing properties.
  • thermoplastic in the continuous phase of a composition according to the invention may be any thermoplastic polymer which is to be protected from a thermo-oxidative attack. These are preferably amorphous polymers, thermoplastic elastomers or semi-crystalline polymers.
  • the stabilizer system according to the invention is particularly preferably used for polymers used in high-temperature applications, very particularly preferably for semi-crystalline thermoplastics having a melting point of at least 180 ° C. or amorphous thermoplastics having a glass transition temperature of at least 180 ° C.
  • Particularly preferred amorphous polymers for compositions according to the invention are amorphous polyamides, polyimides, polyetherimides, polysulfones or polyarylates.
  • Particularly preferred semi-crystalline polymers for compositions according to the invention are polyphenylene sulfides, polyesters, polyether ketones and semi-crystalline polyamides.
  • the thermoplastic may also be a blend of different thermoplastic polymers.
  • the stabilizer system to be used according to the invention for stabilizing semi-crystalline polyamide in particular polyamide 6 or polyamide 66 with relative solution viscosities in m-cresol of 2.0 to 4.0, particularly preferably polyamide 6 with a relative solution viscosity in m- cresol. Cresol used from 2.3-3.2.
  • the transit times of a dissolved polymer are measured by an Ubbelohde viscometer to subsequently determine the difference in viscosity between the polymer solution and its solvent, in this case m-cresol. From this, the viscosity number can be determined taking into account the mass concentration of the polymer solution. The viscosity number can be correlated with the molecular weight of a polymer. By heavy use, z. B. during processing, often occurs a molecular degradation of the polymer. Such an effect can be quantified by determining the viscosity number. Also, molecular changes due to storage in media are detectable by this method. Applicable standards: are DIN 51562; DIN ISO 1628 or equivalent standards.
  • thermoplastic molding compositions according to the invention may also contain blends of the described polyamides and other thermoplastic polymers such as polyphenylene oxide, polyethylene or polypropylene.
  • the polyamides contained in the thermoplastic molding compositions according to the invention can be prepared by various processes and synthesized from different building blocks.
  • For the preparation of polyamides a variety of procedures are known, depending on the desired end product different monomer units, various chain regulators are used to set a desired molecular weight or monomers with reactive groups for later intended aftertreatments.
  • Preferred polyamides according to the invention are partially crystalline polyamides which can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
  • Suitable starting materials are aliphatic and / or aromatic dicarboxylic acids, more preferably adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines, particularly preferably tetramethylenediamine, Hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomers diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bis-aminomethyl-cyclohexane, phenylenediamines, xy
  • caprolactams most preferably ⁇ -caprolactam is used.
  • PA6 PA66 and other compounds based on aliphatic or / and aromatic polyamides or copolyamides, in which 3 to 11 methylene groups are present on a polyamide group in the polymer chain.
  • Further additives for the purposes of the present invention are preferably further heat stabilizers which do not fall under the definition of the stabilizer system to be used according to the invention, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, lubricants, mold release agents, dyes or pigments.
  • UV stabilizers gamma ray stabilizers
  • hydrolysis stabilizers hydrolysis stabilizers
  • antistatic agents emulsifiers
  • nucleating agents plasticizers
  • processing aids impact modifiers
  • lubricants lubricants
  • mold release agents dyes or pigments
  • dyes or pigments preferably further heat stabilizers which do not fall under the definition of the stabilizer system to be used according to the invention
  • UV stabilizers e.g., UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers,
  • Additional heat stabilizers to be used according to the invention which do not fall under the abovementioned definition of the stabilizer system to be used according to the invention are copper compounds, in particular copper halides in combination with alkali metal halides, sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines, in particular diphenylamines, substituted resorcinols, Salicylates, benzotriazoles or benzophenones, as well as various substituted representatives of these groups and / or mixtures thereof.
  • copper compounds in particular copper halides in combination with alkali metal halides, sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines, in particular diphenylamines, substituted resorcinols, Salicylates, benzotriazoles or benzophenones, as well as various substituted representatives of these groups and / or mixtures thereof.
  • UV stabilizers to be used as additives according to the invention are substituted resorcinols, salicylates, benzotriazoles or benzophenones.
  • these are generally copolymers which are preferably composed of at least two of the following series of monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or Methacrylic acid esters having 1 to 18 carbon atoms in the alcohol component.
  • the copolymers may contain compatibilizing groups, preferably maleic anhydride or epoxide.
  • Dyes or pigments preferably to be used as additive according to the invention are inorganic pigments, particularly preferably titanium dioxide, ultramarine blue, iron oxide, zinc sulfide or carbon black, and also organic pigments, more preferably phthalocyanines, quinacridones, perylenes and dyes, more preferably nigrosine or anthraquinones as colorants and other colorants.
  • Nucleating agents preferably to be used according to the invention as an additive are sodium or calcium phenylphosphinate, aluminum oxide or silicon dioxide or talc, particularly preferably talc.
  • Long-chain fatty acids in particular stearic acid, their salts, in particular Ca or Zn stearate and their ester derivatives or amide derivatives, in particular ethylene-bis-stearylamide, glycerol tristearate, stearyl stearate, montan waxes, in particular esters of Montan acids with ethylene glycol and low molecular weight polyethylene or polypropylene waxes in oxidized and non-oxidized form.
  • Inventively particularly preferred lubricants and / or mold release agents are in the group of esters or amides of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols or amines having 2 to 40 carbon atoms. It It is also possible to use mixtures of different lubricants and mold release agents, the mixing ratio being arbitrary.
  • Suitable as lubricants are copolymers of olefins and methacrylic acid esters or of olefins and acrylic esters WO2005 / 121249 A1 or polyhydric alcohols according to EP1041109 A2 in question.
  • thermoplastics already present in polymer form are preferably used.
  • the mixing of components A to C or A to D takes place in the corresponding proportions by weight.
  • the mixing (compounding) of the components at temperatures of 220 to 360 ° C by mixing together, mixing, kneading, compounding, extruding or rolling of the components, more preferably by compounding on a co-currently running twin-screw extruder or Buss kneader. It may be advantageous to premix individual components.
  • the molding compositions to be produced according to the invention can be prepared by processes known to the person skilled in the art. be processed in particular by extrusion, blow molding or injection molding.
  • the present invention therefore also provides a process for the preparation of the molding compositions according to the invention, which comprises mixing components A to C and optionally also D in corresponding proportions by weight, preferably at 220 to 360 ° C., more preferably by mixing, mixing, kneading Compounding, extruding or rolling.
  • the moldings to be produced according to the invention from the molding compositions can preferably be used in the automotive, electrical, electronic, telecommunications, information technology, computer industry, household, sports, medical or entertainment industries.
  • molding compositions according to the invention can be used for applications for which a high stability against heat aging is required. Preferred for such applications is the use for components in vehicles, in particular in motor vehicles (motor vehicles), in particular in the motor vehicle engine compartment.
  • the present invention therefore also relates to the use of molding compositions containing the stabilizer system to be used according to the invention for the production of components and articles with increased stability against thermooxidative damage, preferably of components for motor vehicles, particularly preferably for the engine compartment of motor vehicles.
  • the molding compositions according to the invention are also suitable for applications or components or articles where, in addition to the thermo-oxidative stability, a stability to photo-oxidative damage is required, preferably solar systems.
  • the individual components were mixed in a twin-screw extruder of the type ZSK 32 Compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany) at a temperature of about 280 ° C, discharged as a strand in a water bath, cooled to granulation and granulated. The granules were dried for two days at 70 ° C in a vacuum oven.
  • the granules were subjected to heat aging at 210 ° C in air atmosphere, and the course of aging was followed by measuring the weight loss.
  • the example shows that the percentage mass loss after 672 h aging at 210 ° C of a composition according to the invention is smaller than in Comparative Examples 1 and 2.
EP11174032.0A 2011-07-14 2011-07-14 Masses de formage thermoplastiques dotées d'une stabilité améliorée contre le vieillissement thermique Active EP2546295B1 (fr)

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EP11174032.0A EP2546295B1 (fr) 2011-07-14 2011-07-14 Masses de formage thermoplastiques dotées d'une stabilité améliorée contre le vieillissement thermique

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0535955A1 (fr) * 1991-10-02 1993-04-07 Sumitomo Chemical Company, Limited Composition de résine thermoplastique
EP0566377A1 (fr) * 1992-04-14 1993-10-20 Sumitomo Chemical Company, Limited Compositions de polyphénylène éther résistant à la decoloration
DE4305166A1 (de) 1993-02-19 1994-08-25 Bayer Ag Thermostabile kupferhaltige Polyamidformmassen
US5744056A (en) 1993-07-16 1998-04-28 Amoco Corporation Oxygen-scavenging compositions and articles
EP1041109A2 (fr) 1999-03-30 2000-10-04 Ube Industries, Ltd. Compositions de polyamide ayant une bonne fluidité
US20020001708A1 (en) * 1998-10-20 2002-01-03 Flaherty Kenneth A. Coating compositions having improved hiding powder
WO2002042384A1 (fr) * 2000-11-27 2002-05-30 Basf Coatings Ag Peintures pulverulentes durcissables, procede permettant de les produire et systeme melangeur pour peintures pulverulentes
WO2005007727A1 (fr) 2003-07-18 2005-01-27 Dsm Ip Assets B.V. Composition de moulage a stabilisation thermique
WO2005118722A1 (fr) * 2004-06-01 2005-12-15 Eckart Gmbh & Co. Kg Composition de revetement aqueuse a pigments d'aluminium couvrants, minces et resistants a la corrosion, procede de production et utilisation de ladite composition
WO2005121249A1 (fr) 2004-06-08 2005-12-22 Lanxess Deutschland Gmbh Matieres moulables a base de polyamide, a fluidite amelioree
WO2007017195A2 (fr) * 2005-08-05 2007-02-15 Eckart Gmbh Pigments a effet metallique comprenant une couche mixte inorganique/organique, leur procede de production, et leur utilisation

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0535955A1 (fr) * 1991-10-02 1993-04-07 Sumitomo Chemical Company, Limited Composition de résine thermoplastique
EP0566377A1 (fr) * 1992-04-14 1993-10-20 Sumitomo Chemical Company, Limited Compositions de polyphénylène éther résistant à la decoloration
DE4305166A1 (de) 1993-02-19 1994-08-25 Bayer Ag Thermostabile kupferhaltige Polyamidformmassen
US5744056A (en) 1993-07-16 1998-04-28 Amoco Corporation Oxygen-scavenging compositions and articles
US20020001708A1 (en) * 1998-10-20 2002-01-03 Flaherty Kenneth A. Coating compositions having improved hiding powder
EP1041109A2 (fr) 1999-03-30 2000-10-04 Ube Industries, Ltd. Compositions de polyamide ayant une bonne fluidité
WO2002042384A1 (fr) * 2000-11-27 2002-05-30 Basf Coatings Ag Peintures pulverulentes durcissables, procede permettant de les produire et systeme melangeur pour peintures pulverulentes
WO2005007727A1 (fr) 2003-07-18 2005-01-27 Dsm Ip Assets B.V. Composition de moulage a stabilisation thermique
WO2005118722A1 (fr) * 2004-06-01 2005-12-15 Eckart Gmbh & Co. Kg Composition de revetement aqueuse a pigments d'aluminium couvrants, minces et resistants a la corrosion, procede de production et utilisation de ladite composition
WO2005121249A1 (fr) 2004-06-08 2005-12-22 Lanxess Deutschland Gmbh Matieres moulables a base de polyamide, a fluidite amelioree
WO2007017195A2 (fr) * 2005-08-05 2007-02-15 Eckart Gmbh Pigments a effet metallique comprenant une couche mixte inorganique/organique, leur procede de production, et leur utilisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Plastic Additives Handbook", 2001, CARL HANSER VERLAG, pages: 10 - 19,40-92
"Plastics Additives Handbook", 2001, HANSER-VERLAG, pages: 80 - 84,546-5
HOLLEMANN, WIBERG: "Lehrbuch der Anorganischen Chemie", 1995, DEGRUYTER, pages: 1511 - 1514

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